Carbothermal synthesis of carbon-supported nanoscale zero-valent iron particles for the remediation of hexavalent chromium

Nanoscale, zero-valent iron is a promising reagent for in situ reduction of a variety of subsurface contaminants, but its utility in full-scale remediation projects is limited by material costs. Iron nanoparticles (20-100 nm diameter) supported on carbon (C-Fe⁰) were synthesized by reacting iron salts, adsorbed or impregnated from aqueous solutions onto 80 m²/g carbon black, at 600-800°C under Ar. Similar products were obtained by heating the reactants under air in a covered alumina crucible. X-ray powder diffraction patterns show that Fe₃O₄ particles are formed at 300-500°C in the initial stage of the reaction and that these particles are reduced to a mixture of α- and γ-Fe nanoparticles above 600°C. When C-Fe⁰ was combined with carboxymethylcellulose in a 5:1 weight ratio in water, the resulting material had similar transport properties to previously optimized nanoiron/polyanion suspensions in water-saturated sand columns. At a 10:3 Fe/Cr mole ratio, C-Fe⁰ reduced a 10 ppm Cr(VI) solution to ∼1 ppm within three days. The surface area normalized first-order Cr removal rate was 1.2 h^-1 m^-2 under these conditions. These results demonstrate that reactive nanoiron with good transport properties in water-saturated porous media can be made in a scalable process from inexpensive starting materials by carbothermal reduction.